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Femtosecond and Attosecond Electron-Transfer Dynamics in PCPDTBT:PCBM Bulk Heterojunctions

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journal contribution
posted on 24.05.2018 by F. O. L. Johansson, M. Ivanović, S. Svanström, U. B. Cappel, H. Peisert, T. Chassé, A. Lindblad
Charge separation efficiency is a crucial parameter for photovoltaic devicespolymers consisting of alternating electron-rich and electron-deficient parts can achieve high such efficiencies, for instance, together with a fullerene electron acceptor. This offers a viable path toward solar cells with organic bulk heterojunctions. Here, we measured the charge-transfer times in the femtosecond and attosecond regimes via the decay of sulfur 1s X-ray core-excited states (with the core-hole clock method) in blends of a low-band gap polymer {PCPDTBT [poly­[2,6-(4,4-bis­(2-ethylhexyl)-4H-cyclopenta­[2,1-b;3,4-b′]­dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]]} consisting of a cyclopentadithiophene electron-rich part and a benzothiadiazole electron-deficient part. The constituting parts of the bulk heterojunction were varied by adding the fullerene derivative PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) (weight ratio of polymer/PCBM as 1:0, 1:1, 1:2, and 1:3). For low-energy excitations, the charge-transfer time varies to the largest extent for the thiophene donor part. The charge-transfer time in the 1:2 blend is reduced by 86% compared to that of pristine PCPDTBT. At higher energy excitations, the charge-transfer time does not vary with the chemical environment, as this regime is dominated by intramolecular conduction that yields ultrafast charge-transfer times for all blends, approaching 170 as. We thus demonstrate that the core-hole clock method applied to a series with changing composition can give information about local electron dynamics (with chemical specificity) at interfaces between the constituting partsthe crucial part of a bulk heterojunction where the initial charge separation occurs.